WO2023277192A1

WO2023277192A1 - Sponge cobalt catalyst composition and method for producing same

Info

Publication number: WO2023277192A1
Application number: PCT/JP2022/026528
Authority: WO
Inventors: 啓智山▲崎▼
Original assignee: 日揮触媒化成株式会社
Priority date: 2021-07-02
Filing date: 2022-07-01
Publication date: 2023-01-05
Also published as: JPWO2023277192A1; JP7284879B1

Abstract

[Problem] To provide a sponge cobalt catalyst that exhibits a high catalytic activity even during long-term use. [Solution] A sponge cobalt catalyst composition comprising water, an oxo acid, and a sponge cobalt catalyst, wherein the oxo acid contains W or Mo and all or a portion of the oxo acid is adsorbed to the sponge cobalt catalyst.

Description

Sponge cobalt catalyst composition and method for producing the same

The present invention relates to a sponge cobalt catalyst composition and a method for producing the same.

Sponge metal catalysts, also called Raney (registered trademark) metal catalysts, are a general term for catalysts whose main component is sponge-like active metals. More details are described in Teruo Kubomatsu and Shinichiro Komatsu, "Raney Catalyst", Kyoritsu Shuppan (1971). Sponge metal catalysts form an alloy of metals having catalytic activity (such as nickel, cobalt, copper, iron, silver, and palladium) and eluted metals (such as aluminum, silicon, zinc, and magnesium) to form alloys. It is obtained by a method of eluting eluted metal from (hereinafter also referred to as “developing”). Sponge metal catalysts have many fine pores derived from such a production method, and are utilized in various catalytic reactions by taking advantage of this feature. Sponge cobalt catalysts are one kind of sponge metal catalysts and are widely used as catalysts for hydrogenation reactions. For example, it is used for the hydrogenation reaction of nitriles.

Patent Documents 1 and 2 disclose the use of a sponge cobalt catalyst in the reaction of hydrogenating adiponitrile to synthesize hexamethylenediamine. Further, Patent Documents 3 and 4 disclose the use of a sponge cobalt catalyst in the reaction of hydrogenating phthalonitrile to synthesize xylylenediamine. Furthermore, Patent Document 5 discloses the use of a sponge cobalt catalyst in the reaction of hydrogenating aminoacetonitrile to synthesize ethylenediamine.

JP-A-2001-302595 Japanese Patent Publication No. 2002-529227 JP-A-54-41804 JP 2013-177346 A Japanese Patent Publication No. 2010-520175

The problem with conventional sponge cobalt catalysts is that their catalytic activity tends to decrease after long-term use.

Therefore, an object of the present invention is to provide a sponge cobalt catalyst composition containing a sponge cobalt catalyst with high catalytic activity even when used for a long period of time, and a method for producing the same.

According to one aspect of the present invention, the following sponge cobalt catalyst composition and method for producing the same are provided.
[1] including water, oxoacid, sponge cobalt catalyst,
the oxoacid comprises W or Mo,
part or all of the oxoacid is adsorbed on the sponge cobalt catalyst;
A sponge cobalt catalyst composition.
[2] The sponge cobalt catalyst composition according to [1], wherein the oxoacid containing W is adsorbed on the sponge cobalt catalyst in an amount of 5 mg or more and 1200 mg or less per 1 kg of the sponge cobalt catalyst in terms of W. thing.
[3] The oxoacid containing Mo is adsorbed on the sponge cobalt catalyst in a range of 5 mg or more and 1000 mg or less per 1 kg of the sponge cobalt catalyst in terms of Mo, according to [1] or [2]. A sponge cobalt catalyst composition.
[4] Any one of [1] to [3], wherein the oxoacid is at least one selected from WO ₄ ^2- , MoO ₄ ^2- , Mo ₇ O ₂₄ ^6- and Mo ₈ O ₂₆ ^4- The sponge cobalt catalyst composition according to .
[5] The molar ratio (W/Co) between W contained in the oxoacid adsorbed on the sponge cobalt catalyst and Co contained in the sponge cobalt catalyst is in the range of 0.00001 or more and 0.0005 or less. , the sponge cobalt catalyst composition according to any one of [1] to [4].
[6] The molar ratio (Mo/Co) between Mo contained in the oxoacid adsorbed on the sponge cobalt catalyst and Co contained in the sponge cobalt catalyst is in the range of 0.00001 or more and 0.01 or less. , the sponge cobalt catalyst composition according to any one of [1] to [5].
[7] Any one of [1] to [6], wherein the molar ratio (Mo/W) between W and Mo contained in the oxoacid adsorbed on the sponge cobalt catalyst is in the range of 1 or more and 10 or less. The sponge cobalt catalyst composition according to 1.
[8] The sponge cobalt catalyst composition according to any one of [1] to [7], wherein the content of cobalt contained in the sponge cobalt catalyst is in the range of 30% by mass or more and 70% by mass or less.
[9] The sponge cobalt catalyst composition according to any one of [1] to [8], wherein the content of aluminum contained in the sponge cobalt catalyst is in the range of 30% by mass or more and 70% by mass or less.
[10] The sponge cobalt catalyst composition according to any one of [1] to [9], which is used for hydrogenation of nitrile.
[11] an alloy preparation step of preparing an alloy containing cobalt and aluminum;
a developing step of removing the aluminum from the alloy to obtain a sponge cobalt catalyst;
an immersion step of immersing the sponge cobalt catalyst in water;
A method for producing a sponge cobalt catalyst composition, comprising an adsorption step of adding an oxoacid salt containing W or Mo to the water to cause the sponge cobalt catalyst to adsorb the oxoacid.

1 is an image diagram of the sponge cobalt catalyst composition of the present invention. FIG. Isophthalonitrile contained in the reaction liquid in the activity test using the sponge cobalt catalyst of Examples 1 to 3 (W adsorbed on the sponge cobalt catalyst: 88 to 534 mg/kg-cat) and Comparative Example 1 (no W) It is a graph which shows the relationship between a ratio and the number of times of reaction. Meta-xylylene contained in the reaction liquid in the activity test using the sponge cobalt catalyst of Examples 1 to 3 (W adsorbed on the sponge cobalt catalyst: 88 to 534 mg/kg-cat) and Comparative Example 1 (no W) It is a graph which shows the relationship between an amine ratio and the number of times of reaction. Example 1 (adsorption of oxoacid containing W), Example 4 (adsorption of oxoacid containing Mo), Example 5 (adsorption of oxoacid containing W and oxoacid containing Mo) and Comparative Example 1 (adsorption of oxoacid containing W) 4 is a graph showing the relationship between the ratio of isophthalonitrile contained in the reaction solution and the number of reactions in an activity test using a sponge cobalt catalyst (without acid adsorption). Example 1 (adsorption of oxoacid containing W), Example 4 (adsorption of oxoacid containing Mo), Example 5 (adsorption of oxoacid containing W and oxoacid containing Mo) and Comparative Example 1 (adsorption of oxoacid containing W) 4 is a graph showing the relationship between the ratio of meta-xylylenediamine contained in the reaction liquid and the number of reactions in an activity test using a sponge cobalt catalyst (without acid adsorption).

In order to solve the above-mentioned problems, the inventors investigated the surface state of the sponge cobalt catalyst where the catalytic reaction occurs. Specifically, the inventors have found that by adsorbing an oxoacid containing W or Mo on the surface of a sponge cobalt catalyst, the catalytic activity increases even after long-term use.

The present invention relates to a sponge cobalt catalyst composition containing a sponge cobalt catalyst on which an oxoacid containing W or Mo is adsorbed. The sponge cobalt catalyst composition of the present invention (hereinafter also referred to as "catalyst composition of the present invention") will be described in detail below.

[Catalyst composition of the present invention]
The catalyst composition of the invention comprises water, an oxoacid, and a sponge cobalt catalyst. The sponge cobalt catalyst contained in the catalyst composition of the present invention is present in water because the surface of the sponge cobalt catalyst deteriorates when exposed to the atmosphere. Part or all of the oxoacid present in this water is adsorbed on the surface of the sponge cobalt catalyst (see FIG. 1). The surface of the sponge cobalt catalyst contained in the catalyst composition of the present invention is modified with oxoacid, and it is considered that the catalytic activity increases even after long-term use.

The oxoacid contains W (tungsten) or Mo (molybdenum). The W-containing oxoacid is preferably WO ₄ ^2- . Further, the oxoacid containing Mo is preferably MoO ₄ ^2- , Mo ₇ O ₂₄ ^6- and Mo ₈ O ₂₆ ^4- . The sponge cobalt catalyst having the oxoacid adsorbed on its surface has high catalytic activity even after long-term use. Moreover, the sponge cobalt catalyst adsorbing the oxoacid containing W and the oxoacid containing Mo has higher catalytic activity when used for a long period of time.

Among the oxoacids, the preferred content of the oxoacid adsorbed on the surface of the sponge cobalt catalyst (also referred to as “oxoacid (adsorption)”) is and different. When the oxoacid (adsorption) contains W, the content is preferably 5 mg or more and 1200 mg or less, more preferably 10 mg or more and 300 mg or less, in terms of W, relative to 1 kg of the sponge cobalt catalyst. Particularly preferably, the amount is 20 mg or more and 200 mg or less. When the oxoacid (adsorption) contains Mo, the content is preferably in the range of 5 mg or more and 2000 mg or less, and in the range of 50 mg or more and 1500 mg or less per 1 kg of the sponge cobalt catalyst, in terms of Mo. More preferably, it is particularly preferably in the range of 100 mg or more and 1200 mg or less. When the content of the oxoacid (adsorption) is within the above range, the catalytic activity of the sponge cobalt catalyst tends to be high when used for a long period of time. This content is calculated using a value obtained by subtracting the amount of W and Mo contained in water from the total amount of W and Mo contained in the sponge cobalt catalyst composition of the present invention.

The molar ratio (W/Co) between W contained in the oxoacid (adsorption) and Co contained in the sponge cobalt catalyst is preferably 0.00001 or more and 0.0005 or less, and is preferably 0.00002 or more and 0.00002 or more. 0003 or less is more preferable, and 0.00003 or more and 0.0001 or less is particularly preferable. Further, the molar ratio (Mo/Co) between Mo contained in the oxoacid (adsorption) and Co contained in the sponge cobalt catalyst is preferably 0.00001 or more and 0.01 or less, 0.00005 or more, It is more preferably 0.005 or less, and particularly preferably 0.0001 or more and 0.003 or less. When this molar ratio is within the range described above, the catalytic activity of the sponge cobalt catalyst is high even when used for a long period of time.

When the oxoacid containing W and the oxoacid containing Mo are adsorbed on the surface of the sponge cobalt catalyst, the molar ratio (Mo/W) is preferably 1 or more and 10 or less, more preferably 1 or more and 7 or less. 1 or more and 5 or less are particularly preferable. When this molar ratio is within the range described above, the catalytic activity of the sponge cobalt catalyst is high even when used for a long period of time.

The sponge cobalt catalyst is spongy by removing part of Al from an alloy containing Co (cobalt) and Al (aluminum). By becoming spongy, the metal surface of Co increases and the catalytic activity also increases.

The content of Co contained in the sponge cobalt catalyst is preferably in the range of 30% by mass or more and 70% by mass or less, more preferably in the range of 40% by mass or more and 60% by mass or less, and 50% by mass. % or more and 60 mass % or less is particularly preferable. When the content is within the above range, the initial activity of the sponge cobalt catalyst tends to be high.

The sponge cobalt catalyst preferably contains Al. The Al content of the catalyst of the present invention is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less, and 50% by mass or more and 60% by mass or less. is particularly preferred.

The sponge cobalt catalyst is preferably granular. In the present invention, agglomerates having a minor axis and a major axis of less than 1 mm are defined as powder, and other agglomerates are defined as grains. The sponge cobalt catalyst exhibits the effects of the invention whether it is in the form of granules or powder, and particularly in the form of granules. A granular sponge cobalt catalyst tends to have a smaller outer surface area than a powdery sponge cobalt catalyst, and its catalytic activity tends to decrease when used for a long period of time. However, since the sponge cobalt catalyst has the oxoacid adsorbed on its surface, its catalytic activity is high even after long-term use. Further, the granular sponge cobalt catalyst can be used as a fixed bed catalyst, and the catalyst and the product can be easily separated, so that the productivity is excellent. More preferably, the sponge cobalt catalyst has a grain size (particle size) in the range of 1 mm or more and 5 mm or less. The grain size can be determined by the opening of the sieve. For example, when the catalyst of the present invention is sieved using a sieve with a mesh size of 1 mm, it can be determined that the particles above the sieve have a size of 1 mm or more, and the particles below the sieve have a size of less than 1 mm.

The water has a role of protecting the surface of the sponge cobalt catalyst and a medium for adsorbing the oxoacid to the sponge cobalt catalyst. Therefore, the content of the water should be contained to such an extent that the surface of the sponge cobalt catalyst is covered. For example, as shown in FIG. 1, it is preferable that the entire sponge cobalt catalyst is submerged in water. Therefore, the amount of water is appropriately adjusted depending on the amount of sponge cobalt catalyst.

The proportion of oxoacid contained in the water is preferably 50% or less, more preferably 40% or less, relative to the total amount of oxoacid contained in the catalyst composition of the present invention. Not all of the oxoacid contained in the catalyst composition of the present invention is adsorbed on the sponge cobalt catalyst, and some of it may remain in the water due to adsorption equilibrium. Since the water and the sponge cobalt catalyst are separated when the catalyst composition of the present invention is used, even if the water contains oxoacid, there is no significant effect. However, since it may cause problems in waste water treatment, etc., the smaller the ratio, the better.

The pH of the water is preferably 8 or higher, more preferably 8.5 or higher, and particularly preferably 9 or higher. When the pH is within this range, the surface of the sponge cobalt catalyst is positively charged, so that negatively charged oxoacids are more likely to be adsorbed.

The catalyst composition of the present invention may contain ammonium ions or alkali ions in addition to W, Mo, Co and Al. These ions may be included as counter cations of the oxoacid. It may also be contained as ions derived from the alkali used when preparing the sponge cobalt catalyst.

The catalyst composition of the present invention may contain components other than W, Mo, Co, Al, ammonium ions, and alkali ions in the range of 10% by mass or less. For example, elements such as C (carbon), Si (silicon), Mg (magnesium), Ca (calcium) that are easily mixed, and elements that function as promoters such as nickel, molybdenum, zirconium, copper, chromium, iron and manganese may contain Specifically, the content of the easily mixed element is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. In addition, the component that functions as a cocatalyst is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and 0.1% by mass. Above, it is especially preferable that it is 3 mass % or less.

INDUSTRIAL APPLICABILITY The catalyst composition of the present invention can be used in a wide range of fields as long as it is used in fields where cobalt catalysts are used. For example, it can be used as a catalyst for hydrogenation reactions. Known hydrogenation reactions include carbon-carbon double bond, carbon-carbon triple bond, benzene nucleus, pyridine, carbonyl group, nitro group, nitrile, fatty acid and ester reactions. The catalyst of the present invention can be suitably used as a catalyst for the hydrogenation reaction of nitriles. When using the catalyst composition of the present invention in these applications, the water is removed to remove the sponge cobalt catalyst. At this time, the oxoacid adsorbed on the surface of the sponge cobalt catalyst is considered to form a salt with a counter cation contained in water. For example, when an oxoacid containing W is adsorbed on a sponge cobalt catalyst and sodium ions are present as counter cations, it is considered that Na ₂ WO ₄ is formed on the surface of the sponge cobalt catalyst.

[Method for producing the catalyst composition of the present invention]
The method for producing the catalyst composition of the present invention (hereinafter also referred to as the “production method of the present invention”) comprises an alloy preparation step of preparing an alloy containing Co and Al, removing the Al from the alloy to produce a sponge cobalt catalyst. an immersion step of immersing the sponge cobalt catalyst in water; and an adsorption step of adding an oxoacid salt containing W or Mo to the water to cause the sponge cobalt catalyst to adsorb the oxoacid. The manufacturing method of the present invention will be described in detail below.

[Alloy preparation process]
The alloy can be prepared by a conventionally known method. For example, it can be prepared by mixing and melting metal Co and metal Al. The content of Co contained in the alloy is preferably 20% by mass or more and 70% by mass or less, and more preferably 30% by mass or more and 60% by mass or less. Also, the content of Al contained in the alloy is preferably 30% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 70% by mass or less. In the production method of the present invention, part of the Al contained in the alloy is removed in the expansion step described later, and the place where the Al was present becomes a cavity, forming a spongy cobalt alloy. Therefore, the more Al contained in the alloy, the more cavities are likely to increase, but the strength is likely to decrease. Therefore, the content of Co and the content of Al in the alloy are preferably within the ranges described above.

The alloy preparation step preferably includes a grain size adjustment step of adjusting the grain size of the alloy. Specifically, it is preferable to pulverize the alloy and adjust the grain size to 1 mm or more and 5 mm or less. Adjusting the grain size of the alloy in this way makes it easier to remove Al in the expansion step, which will be described later, and increases the production efficiency.

[Development process]
A conventionally known method can be used to remove Al from the alloy. For example, a method of treating the alloy with an alkaline solution can be used. When an alkaline solution is used, the type of alkali is not particularly limited, and conventionally known alkalis such as alkali hydroxides and alkali carbonates can be used. More specifically, sodium hydroxide or potassium hydroxide is preferably used. Further, the alkali content of the alkali solution is preferably 0.01 times or more and 3 times or less in molar ratio with respect to the Al content in the alloy. Al in the alloy can be efficiently removed when the alkali amount of the alkaline solution is within the above range. In addition, when the removal of Al is insufficient, the Al may be removed to the target level by increasing the number of treatments. Furthermore, when Al is left in the alloy, the amount of alkali in the alkaline solution is preferably 0.1 to 1 times the amount of Al in the alloy.

In the developing step, the developing temperature is preferably 10°C or higher and less than 100°C, and more preferably 20°C or higher and 90°C or lower. As the developing temperature increases, Al becomes easier to dissolve. However, if Al is rapidly eluted, the expanded sponge cobalt catalyst tends to collapse. Also, the expansion time may be appropriately adjusted depending on the degree of removal of Al. Although it depends on the amount of treatment, Al can be removed without any problem if it is 0.5 hours or more and 12 hours or less.

[Immersion process]
By immersing the sponge cobalt catalyst obtained in the developing step in water, the surface of the sponge cobalt catalyst is protected. Water also serves as a medium for adsorbing the oxoacid on the surface of the sponge cobalt catalyst.

The immersion step may include a washing step for washing the sponge cobalt catalyst. For example, the sponge cobalt catalyst may be immersed in water after being washed by passing water through it. The temperature of water when washing the sponge cobalt catalyst is preferably 20° C. or higher and 60° C. or lower, and more preferably 30° C. or higher and 50° C. or lower. Washing with water at such a temperature facilitates removal of soluble impurities contained in the sponge cobalt catalyst.

The immersion step preferably includes a pH adjustment step. By adjusting the pH to 8 or higher, preferably 8.5 or higher, and particularly preferably 9 or higher, the oxoacid is more likely to be adsorbed on the surface of the sponge cobalt catalyst in the adsorption step described later. A conventionally known method can be used for adjusting the pH. For example, the pH can be adjusted by adding a basic compound such as ammonia, sodium hydroxide or potassium hydroxide.

[Adsorption process]
A conventionally known method can be used as a method of adding an oxoacid salt containing W or Mo to the water to cause the sponge cobalt catalyst to adsorb the oxoacid. For example, _oxoacid _salts such as _Na2WO4 , _K2WO4 , _Na2MoO4 , _Mo7O24 ₍ _NH4 ₎ ₆ may be added to the water. At this time, the temperature of the aqueous solution containing the oxoacid is preferably 10° C. or higher and 100° C. or lower, and more preferably 10° C. or higher and 50° C. or lower. The time for performing these treatments depends on the amount of treatment, but if it is 1 hour or more and 24 hours or less, the oxoacid can be adsorbed on the surface of the sponge cobalt catalyst without any problem.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
[Measurement method or evaluation method]
Various measurements and evaluations were performed as follows.

[1] Composition Analysis A measurement sample was collected in a beaker, and after adding hydrochloric acid and nitric acid and heating, water was added to dissolve the sample. Furthermore, after diluting this with water, the contents of Co, Al, W and Mo were measured using an ICP device (manufactured by Agilent Technologies, 730ICP-OES, inductively coupled plasma emission spectrometry). The amount of oxoacid containing W or Mo adsorbed on the sponge cobalt catalyst was calculated by subtracting the amount of oxoacid contained in water from the total amount of oxoacid contained in the catalyst composition.

[2] Activity test A nitrile hydrogenation activity test was performed with reference to the method described in the example of JP-A-54-41804. Specifically, a 330 mL autoclave was charged with 8 g of isophthalonitrile, 24 mL of methanol, 96 mL of toluene, 3 g of a measurement sample (sponge cobalt catalyst) and 1 g of an aqueous sodium hydroxide solution (50% by mass), hydrogen pressure of 8 MPa, reaction temperature of 70° C., The reaction was carried out for 6 hours at a stirring speed of 900 rpm. After the reaction, the measurement sample was removed and the reaction liquid was analyzed by gas chromatography. From the resulting chart, isophthalonitrile and m-xylylenediamine peaks were separated, and the ratio of each component to all peak areas included in the chart was determined.

[Example 1]
CoAl alloy grains (size: 1 mm or more and 5 mm or less) composed of 40% by mass of cobalt and 60% by mass of aluminum were developed and washed with sodium hydroxide to obtain a sponge cobalt catalyst. After the expanded sponge cobalt catalyst was immersed in water, the pH was measured at 25° C. and found to be 10. After that, an aqueous solution containing 150 ppm of Na ₂ WO ₄ (Na ₂ WO ₄ .2H ₂ O: manufactured by Wako Pure Chemical Industries, Ltd., special reagent grade) was added at room temperature to the weight of the sponge cobalt catalyst (weight in water). , The aqueous solution containing 150 ppm of Na ₂ WO ₄ refers to an aqueous solution containing 150 ppm of W derived from Na ₂ WO _4. Converting this to the amount of Na ₂ WO ₄ added to 1 kg of sponge cobalt catalyst, 240 mg ). Then, after standing for 12 hours or longer, a sponge cobalt catalyst composition was obtained. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Further, the results of activity tests are shown in FIGS. 2, 3, 4 and 5. FIG.

[Example 2]
A sponge cobalt catalyst composition was obtained in the same manner as in Example 1, except that the amount of Na ₂ WO ₄ added to 1 kg of the sponge cobalt catalyst was 150 mg. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Furthermore, the results of the activity test are shown in FIGS. 2 and 3. FIG.

[Example 3]
A sponge cobalt catalyst composition was obtained in the same manner as in Example 1, except that the amount of Na ₂ WO ₄ added to 1 kg of the sponge cobalt catalyst was 1,600 mg. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Furthermore, the results of the activity test are shown in FIGS. 2 and 3. FIG.

[Example 4]
Na ₂ WO ₄ was changed to Mo ₇ O ₂₄ (NH ₄ ) ₆ (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade), and the amount of Mo ₇ O ₂₄ (NH ₄ ) ₆ added to 1 kg of sponge cobalt catalyst was 240 mg. A sponge cobalt catalyst composition was obtained in the same manner as in Example 1, except for the above. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Furthermore, the results of the activity test are shown in FIGS. 4 and 5. FIG.

[Example 5]
A sponge cobalt catalyst composition was prepared in the same manner as in Example 1, except that Na ₂ WO ₄ and Mo ₇ O ₂₄ (NH ₄ ) ₆ were added, and the amount added was 240 mg per 1 kg of the sponge cobalt catalyst. got Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Furthermore, the results of the activity test are shown in FIGS. 4 and 5. FIG.

[Example 6]
A sponge cobalt catalyst composition was obtained in the same manner as in Example 1, except that Na ₂ WO ₄ was changed to K ₂ WO ₄ (manufactured by Wako Pure Chemical Industries, Ltd., reagent). Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results.

[Example 7]
A sponge cobalt catalyst composition was obtained in the same manner as in Example 4, except that the amount of Mo ₇ O ₂₄ (NH ₄ ) ₆ added to 1 kg of the sponge cobalt catalyst was 1000 mg. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results.

[Comparative Example 1]
A sponge cobalt catalyst composition was obtained in the same manner as in Example 1, except that Na ₂ WO ₄ was not added. Table 1 shows the charged composition of the obtained sponge cobalt composition and the properties obtained by composition analysis and the like. An activity test was also conducted on the sponge cobalt catalyst separated from this catalyst composition. Table 1 shows the results. Further, the results of activity tests are shown in FIGS. 2, 3, 4 and 5. FIG.

From the results of FIG. 2, the sponge cobalt catalyst of Example 1, in which _WO4 is adsorbed, has a lower proportion of isophthalonitrile in the reaction liquid than the sponge cobalt catalyst of Comparative Example 1, in which _WO4 is not adsorbed. . The isophthalonitrile contained in the reaction solution remained unreacted, and the less isophthalonitrile contained in the reaction solution, the more isophthalonitrile reacted. is high. Therefore, the sponge cobalt catalyst of Example 1 is considered to have higher catalytic activity than the sponge cobalt catalyst of Comparative Example 1. Furthermore, by continuing to use this, the difference becomes more remarkable, and when looking at the isophthalonitrile ratio after 5 times of reaction, the isophthalonitrile ratio of Comparative Example 1 is about 6%, The isophthalonitrile proportion in Example 1 is about 1%.

In addition to the results of FIG. 2, as shown in the results of FIG. 3, the ratio of meta-xylylenediamine obtained by hydrogenating isophthalonitrile was also compared with that of Comparative Example 1 when the sponge cobalt catalyst of Example 1 was used. It can be seen that the amount of meta-xylylenediamine produced is greater than in the case of using the sponge cobalt catalyst.

From the results of FIGS. 4 and 5, the sponge cobalt catalyst of Example 4 with Mo ₇ O ₂₄ adsorbed was compared with the sponge cobalt catalyst of Comparative Example 1 without Mo ₇ O ₂₄ adsorbed after 5 reactions. It can be seen that, like the sponge cobalt catalyst of Example 1 with WO ₄ adsorbed, the sponge cobalt catalyst with Mo ₇ O ₂₄ adsorbed has high catalytic activity even after long-term use. . Further, the sponge cobalt catalyst of Example 5 with _WO4 and _Mo7O24 adsorbed was compared to the sponge cobalt catalyst of Example ₁ with _WO4 adsorbed and the sponge cobalt catalyst of Example ₄ with _Mo7O24 adsorbed. As a result, the catalytic activity after 5 reactions is high.

Claims

Contains water, oxoacid, sponge cobalt catalyst,
the oxoacid comprises W or Mo,
part or all of the oxoacid is adsorbed on the sponge cobalt catalyst;
A sponge cobalt catalyst composition.
The sponge cobalt catalyst composition according to claim 1, wherein the oxoacid containing W is adsorbed on the sponge cobalt catalyst in a range of 5 mg or more and 1200 mg or less per 1 kg of the sponge cobalt catalyst in terms of W.
The sponge cobalt catalyst composition according to claim 2, wherein the oxo acid containing Mo is adsorbed on the sponge cobalt catalyst in a range of 5 mg or more and 1000 mg or less per 1 kg of the sponge cobalt catalyst in terms of Mo.
4. The sponge cobalt catalyst composition according to claim 3, wherein the oxoacid is at least one selected from WO 4 2- , MoO 4 2- , Mo 7 O 24 6- and Mo 8 O 26 4- .
The molar ratio (W/Co) between W contained in the oxoacid adsorbed on the sponge cobalt catalyst and Co contained in the sponge cobalt catalyst is in the range of 0.00001 or more and 0.0005 or less. 5. The sponge cobalt catalyst composition according to 4.
The molar ratio (Mo/Co) between Mo contained in the oxoacid adsorbed on the sponge cobalt catalyst and Co contained in the sponge cobalt catalyst is in the range of 0.00001 or more and 0.01 or less. 5. The sponge cobalt catalyst composition according to 5.
The sponge cobalt catalyst composition according to claim 6, wherein the molar ratio (Mo/W) of W and Mo contained in the oxoacid adsorbed on the sponge cobalt catalyst is in the range of 1 or more and 10 or less.
The sponge cobalt catalyst composition according to claim 7, wherein the content of cobalt contained in the sponge cobalt catalyst is in the range of 30% by mass or more and 70% by mass or less.
The sponge cobalt catalyst composition according to claim 8, wherein the content of aluminum contained in the sponge cobalt catalyst is in the range of 30% by mass or more and 70% by mass or less.
The sponge cobalt catalyst composition according to any one of claims 1 to 9, which is used for a reaction of hydrogenating nitrile.
an alloy preparation process to prepare an alloy containing cobalt and aluminum;
a developing step of removing the aluminum from the alloy to obtain a sponge cobalt catalyst;
an immersion step of immersing the sponge cobalt catalyst in water;
A method for producing a sponge cobalt catalyst composition, comprising an adsorption step of adding an oxoacid salt containing W or Mo to the water to cause the sponge cobalt catalyst to adsorb the oxoacid.